KR20230078169A - Flooring material - Google Patents

Abstract

base layer; and a cured layer of an acrylic resin composition having a plurality of alumina particles protruding on the surface thereof, wherein the protruding alumina particles have an average protrusion height of 5 μm to 10 μm.

Description

Flooring {FLOORING MATERIAL}

The present invention relates to flooring.

In general, flooring material provides a hygienic space by blocking dust and cold air from the cement floor, and also has a decorative effect such as changing the indoor atmosphere to a cozy one according to the customer's taste because it is printed with beautiful patterns in various colors. Due to the decorative effect of these flooring materials, the demand for matte flooring is increasing these days.

And, since the user cannot easily erase the traces of the contaminants when the surface of the conventional flooring is dirty with contaminants, the flooring with contaminants cannot fulfill its basic function. In order to overcome this problem, by forming a surface treatment layer on the uppermost layer of the flooring, it is intended to impart fouling resistance.

Conventional flooring has a problem in that contaminants are easily removed when the gloss is high, but contamination resistance is rapidly reduced when the gloss is low. Accordingly, attempts have been made to impart stain resistance and matte properties at the same time, but in this case, there is a problem in that scratch resistance is lowered.

Therefore, there is an urgent need to develop a flooring material having excellent stain resistance and scratch resistance at the same time while implementing a matte flooring material.

An object of the present invention is to provide a flooring material exhibiting excellent matt properties, stain resistance and scratch resistance at the same time.

The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned above can be understood by the following description and will be more clearly understood by the examples of the present invention. It will also be readily apparent that the objects and advantages of the present invention may be realized by means of the instrumentalities and combinations indicated in the claims.

Base layer according to the present invention; and a hardened layer of an acrylic resin composition having alumina particles protruding on the surface thereof, wherein the alumina has an average protruding height of 5 μm to 10 μm.

The flooring material according to the present invention may simultaneously exhibit stain resistance and scratch resistance along with excellent matte properties.

In addition to the effects described above, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.

1 is a schematic diagram briefly showing a cross section of a flooring material according to an embodiment of the present invention.
2 is an image showing the height of protruding alumina particles as a result of scanning electron microscope (SEM) analysis of the surface of a flooring specimen according to an embodiment of the present invention.
3 is an image showing the distance between protruding alumina particles as a result of scanning electron microscope (SEM) analysis of the surface of a flooring specimen according to an embodiment of the present invention.

The above objects, features and advantages will be described later in detail with reference to the accompanying drawings, and accordingly, those skilled in the art to which the present invention belongs will be able to easily implement the technical spirit of the present invention. In describing the present invention, if it is determined that the detailed description of the known technology related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

Hereinafter referred to as the "top (or bottom)" of a component or disposed adjacent to the top (or bottom) surface of the component, as well as between the component and any component disposed on (or below) the component. It may mean that other configurations may be intervened.

Hereinafter, flooring materials according to some embodiments of the present invention will be described.

In one embodiment of the present invention, the base layer; and a cured layer of an acrylic resin composition having a plurality of alumina particles protruding on the surface thereof, wherein the protruding alumina particles have an average height of 5 μm to 10 μm.

Flooring provides a hygienic space and also has a decorative effect that changes the interior atmosphere according to customer tastes. Accordingly, there is a problem in that stain resistance is lowered in the case of trying to impart matt characteristics to the flooring material, but when the glossiness is low. For example, a matting agent such as silica is generally used in a surface treatment layer located at the outermost layer to lower the gloss of a flooring material. As the content of silica increases, the glossiness may decrease, but there is a problem in that contamination resistance rapidly decreases because fine dust, moisture, oil stains, etc. are easily adsorbed.

In addition, there are cases in which a material such as silica is not used a lot, but instead of forming wrinkles on the surface of the surface treatment layer to impart matte properties, in this case, there is a problem in that scratch resistance is lowered.

Therefore, the flooring material of the present invention controls the surface structure of the cured layer, which is the surface treatment layer located in the outermost layer, to exhibit improved matt properties, while simultaneously improving scratch resistance and stain resistance, which are in a trade-off relationship with matt. can make it

1 is a schematic diagram showing a cross section of a flooring material according to an embodiment of the present invention. As shown in Figure 1, the flooring material of the present invention includes a cured layer 20, which is a cured product of an acrylic resin composition, on the base layer 10 as an outermost layer, and the cured layer has a specific structure on the surface. By having a certain structure on the surface of the cured layer, the flooring material can be controlled to simultaneously have excellent physical properties such as remarkably excellent matte properties, scratch resistance, stain resistance, etc. while maintaining a certain level or more of coating properties on the base layer.

Specifically, the hardened layer includes a plurality of alumina particles 30 protruding at a certain height on the surface. 2 is an image showing the height of protruding alumina particles as a result of scanning electron microscope (SEM) analysis of the surface of a flooring material according to an embodiment of the present invention. The height of the alumina means the distance from the upper surface of the hardened layer to the most convex protruding point of the protruding alumina particles. For example, it means the vertical distance from the tangent of the highest point in the protruding part to the point of the hardened layer where the curve constituting the protruding part of the alumina is incorporated into the upper surface of the hardened layer. For example, when the points of the cured layer incorporated into the upper surface of the cured layer vary from location to location due to wrinkles (not shown) on the surface of the cured layer, the average point of each point of the cured layer incorporated into the upper surface of the cured layer Based on , the vertical distance from the tangent line of the highest point in the protruding portion of alumina to the average point may be the height of alumina. The height may be measured by scanning electron microscopy (SEM) analysis, and each of the alumina particles may protrude from the upper surface of the cured layer to a height of about 19 μm or less, for example, greater than about 0 to about 19 μm.

Specifically, the protrusion average height of the plurality of alumina particles protruding from the surface of the cured layer is about 5 μm to about 10 μm. For example, the average protruding height of the alumina may be about 7 μm to about 10 μm. When the average height is less than the above range, the shape such as the height of wrinkles on the surface of the cured layer formed around the protruding alumina is changed, resulting in lowered roughness of the surface of the cured layer, lowered scratch resistance, and lowered non-slip property. There is a problem of losing, and if it exceeds the above range, there is a problem that the coating property is deteriorated and cannot be used as a flooring material. The average protruding height of the alumina means an average value obtained by dividing the protruding height of each protruding alumina by the number of protruding alumina particles.

In the case where the outermost layer of the flooring material includes materials such as polyolefin beads such as polypropylene or glass beads other than alumina, even if the materials protrude to the surface of the outermost layer by the height, sufficient scratch resistance cannot be imparted.

The alumina particles included in the cured layer may have an excellent hardness of about 8 to 9, thereby further improving scratch resistance and implementing excellent durability.

An average distance between the alumina particles protruding from the surface of the cured layer may be greater than or equal to about 50 μm and less than about 180 μm. 3 is an image showing the distance between protruding alumina particles as a result of scanning electron microscope (SEM) analysis of the surface of a flooring specimen according to an embodiment of the present invention. As shown in FIG. 3, the distance between the protruding alumina particles may mean the distance between any one alumina particle protruding on the surface and the alumina particle protruding at the closest position. For example, it can be obtained by measuring the shortest length from the point where the protrusion and curve of any one alumina particle protruding on the surface of the hardened layer is formed from the upper surface of the hardened layer to the point where the protrusion and curve of another alumina particle is formed.

Accordingly, an average distance obtained by averaging distances between alumina particles may be about 50 μm or more and about 180 μm or less. The flooring material can maintain excellent coating properties by adjusting the distance between alumina protruding on the surface of the cured layer within the above range, while improving excellent mattness, scratch resistance, adhesion to the base layer and non-slip properties. For example, when the average distance between the protruding alumina particles on the surface of the hardened layer is less than the above range, scratch resistance can be more easily improved. However, since the content of alumina is too high, the viscosity may increase, as well as too much alumina protruding on the surface, resulting in deterioration in coatability and deterioration in adhesion to the substrate layer. In addition, when the average distance between the protruding alumina particles exceeds the above range, the shape such as the height of wrinkles around the protruding alumina is changed, the roughness of the surface of the hardened layer is lowered, the glossiness is increased, and the scratch resistance is increased. And there may be a problem of deteriorating non-wetting properties.

The average particle diameter (D50) of the alumina particles may be about 25 μm to about 50 μm. The average particle diameter (D50) is defined as the particle diameter at the point of 50% of the cumulative curve of the particle size distribution when the total weight of the aluminum particles is 100%. The particle size can be measured through a particle size analyzer

The cured layer may include alumina particles having the above size to control the height of the alumina protruding from the surface of the cured layer, exhibit excellent scratch resistance and non-slip properties without increasing viscosity or deteriorating stain resistance. For example, when the size of the alumina particles is less than the above range, the height of the alumina particles protruding to the surface of the cured layer may be low, the roughness of the surface of the cured layer may be low, scratch resistance may be lowered, and non-slip properties may be lowered. . In addition, when the size of the alumina particles is smaller than the above range, a kind of matting agent may be implemented, but there may be a problem of increasing the viscosity. In addition, when the size of the alumina particles exceeds the above range, the height of the alumina protruding to the surface of the cured layer increases and coating properties may deteriorate.

The alumina may be included in an amount of about 15 parts by weight to about 30 parts by weight based on 100 parts by weight of the cured layer. When the content of alumina is less than the above range, the average distance between the alumina particles protruding on the surface of the cured layer becomes too far, and thus scratch resistance may be lowered, glossiness may be increased, and non-slip properties may be lowered. In addition, the distribution of the protruding alumina particles becomes too non-uniform, and accordingly, the shape of the wrinkles on the surface also becomes non-uniform, thereby reducing the expression of uniform matt characteristics. And, when the content of alumina exceeds the above range, there may be a problem in that the coating property is deteriorated because there are too many alumina particles protruding on the surface.

In addition, the cured layer may have an average surface roughness (Ra) of about 2 μm to about 4 μm on the surface of the cured layer excluding protruding alumina particles. Surface roughness means "surface roughness" due to wrinkles on the surface of the hardened layer formed on the substrate layer, excluding alumina protruding on the surface. The surface roughness may be a value measured according to center line average roughness (Ra) according to KS B 0161.

The hardened layer may include wrinkles formed on the surface by a method of manufacturing a flooring material containing the alumina particles, and the wrinkles may be observed over the entire surface of the hardened layer, and one can be specified. Surface wrinkles may be formed while having a shape in which a plurality of wrinkles branch in different directions from a point.

The alumina particles protruding from the surface of the hardened layer may be involved in the formation of the wrinkles and affect the shape and size of the wrinkles. Specifically, the average surface roughness (Ra) on the surface of the hardened layer, excluding the alumina protruding from the surface of the hardened layer, is about 2 μm to about 4 μm, and may have a uniform roughness over the entire hardened layer. Accordingly, by inducing scattering of light incident on the surface of the cured layer, it is possible to implement a remarkably low gloss level without using or using a small amount of a matting agent such as silica.

The properties of the surface of the cured layer and physical properties of the flooring material may be influenced by the acrylic resin composition forming the cured layer. Specifically, the acrylic resin composition may include an acrylic monomer, a urethane acrylic oligomer, a silicon-containing acrylic oligomer, a photoinitiator, and the alumina. At this time, an oligomer imparting toughness to the oligomer may be used, the degree of curing may be increased by adjusting the monomers, etc., the alumina particles may be prevented from falling off, and excellent scratch resistance may be exhibited even under harsh conditions.

Specifically, the acrylic monomer may include a monofunctional and/or multifunctional acrylic monomer. Here, monofunctionality and multifunctionality may be classified according to the number of acryl groups included in the compound. For example, when two or more acryl groups are present in a compound, it may be classified as multifunctional.

Specifically, as the acrylic monomer, elongation may be improved by including a monofunctional acrylic monomer (first monomer) containing a straight-chain or branched alkyl group having 5 to 30 carbon atoms and an acryl group. For example, the acrylic resin composition is a monofunctional acrylic monomer that includes caprolactone acrylate, nonylphenol (EO) 8 acrylate, isodecyl acrylate, Selected from the group consisting of lauryl acrylate, 2 (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, and combinations thereof may contain one.

In addition, as the acrylic monomer, a bifunctional acrylic monomer (second monomer) may be included to improve strength, and processability may be improved by controlling viscosity and cutability. For example, as the bifunctional acrylic monomer, 1, 6-hexanediol diacrylate (1, 6-Hexanediol Diacrylate), 1, 6-hexanediol (EO) n diacrylate (1, 6-Hexanediol ( EO)n Diacrylate), hydroxyl pivalic acid neophentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and these It may include one selected from the group consisting of combinations of.

In addition, the acrylic resin composition may include a urethane acrylic oligomer and a silicon-containing oligomer as an oligomer.

The acrylic resin composition has an advantage in that there is no problem with respect to yellowing due to benzenring, compared to coating agents for flooring materials including urethane acrylic oligomers and epoxy acrylic oligomers. In addition, the urethane-acrylic oligomer included in the acrylic resin composition rapidly undergoes radical polymerization by the initiation reaction of the photoinitiator and provides a cured layer with excellent elasticity and toughness, especially for a base layer containing polyvinyl chloride resin (PVC) It can show excellent adhesion.

Specifically, the strength can be improved by including a difunctional urethane acrylate oligomer (first oligomer) having a weight average molecular weight of 1,000 g / mol to 2,000 g / mol as the urethane acrylic oligomer, and a weight average molecular weight of 4,000 g / mol to 6,000 g/mol of a difunctional urethane acrylate oligomer (second oligomer) to improve elongation.

In addition, as the urethane acrylic oligomer, a trifunctional urethane acrylate oligomer (third oligomer) having a weight average molecular weight of 6,000 g/mol to 8,000 g/mol is included to impart toughness to the surface of the cured layer while improving elongation. . Accordingly, it is possible to prevent the alumina protruding from the surface from falling off. The weight average molecular weight may be a value measured through gel permeation chromatography (GPC) measurement.

In addition, by including a silicon acrylate oligomer (fourth oligomer) as the silicon-containing oligomer, strength may be adjusted and stain resistance and scratch resistance may be improved.

Here, the acrylic resin composition includes 20 to 25 parts by weight of the first monomer and 10 to 15 parts by weight of the second monomer, based on 100 parts by weight of the acrylic resin composition, and 10 to 15 parts by weight of the first oligomer and the second oligomer 3 to 7 parts by weight, 10 to 15 parts by weight of the third oligomer, and 10 to 15 parts by weight of the fourth oligomer. At this time, when the content of the monomer is less than the above range and the content of the oligomer exceeds the above range, the effect provided by each material is not exhibited, and the photopolymerization reaction rate is lowered, making it difficult to control the crosslinking density, and the cured layer A large amount of UV irradiation for curing is required, or the UV irradiation time is prolonged, so that the physical properties of the cured layer may be deteriorated, and the viscosity may be too high, resulting in poor coating properties. In addition, when the content of the monomer exceeds the above range and the content of the oligomer is below the above range, the effects provided by each material are not exhibited, and as the photopolymerization reaction proceeds rapidly, the crosslinking density increases and the brittleness of the coating film increases. There is a problem of poor adhesion, and the viscosity is too low, and there is a concern that the coating liquid flows down during the coating process and the coating property is deteriorated. In particular, when the content of the trifunctional urethane acrylate oligomer is less than the above range, alumina particles protruding from the surface may easily fall off, resulting in reduced scratch resistance under harsh conditions, resulting in poor long-term scratch resistance.

In addition, the acrylic resin composition may include a photoinitiator in an amount of about 0.5 parts by weight to about 7 parts by weight based on 100 parts by weight of the composition. And, the alumina is as described above.

The acrylic resin composition may include an additive selected from the group consisting of an antifoaming agent, a leveling agent, a dispersing agent, a wetting agent, and combinations thereof.

The flooring material having the specific structure on the surface of the cured layer of the acrylic resin composition may have a surface gloss of about 3 or less under a gloss 60 ° condition using a gloss meter. The flooring material can implement a remarkably low gloss within the above range without including a very small amount of a matting agent in the hardening layer or not including it at all by inducing scattering of light incident on the surface through the structure of the surface of the hardening layer. Accordingly, it is possible to reduce the user's eye fatigue along with an excellent decorative effect.

The flooring material may exhibit excellent scratch resistance while exhibiting excellent matte characteristics as described above by having the above surface characteristics. Specifically, the flooring material may exhibit excellent scratch resistance of B2 grade or less in micro scratch resistance evaluation according to EN 16094 B procedure.

In addition, in the micro scratch resistance evaluation according to EN 16094 B procedure, using a 6N weight instead of a 4N weight can show excellent scratch resistance of B3 grade or less even under harsher conditions. Accordingly, it can be used for flooring in places exposed to a lot of scratches.

In addition, the flooring material may have a slip resistance BPN (wet, 96 slider) of 45 or more according to ASTM E303. The higher the BPN number, the non-slippery property is exhibited, and the BPN of the flooring material is 45 or more, which may exhibit excellent nonslip property.

The thickness of the cured layer may be adjusted within an appropriate range that does not affect durability. For example, the hardened layer may have an average thickness of about 5 μm to about 25 μm so as not to be torn or lost due to external stimulation. The thickness of the cured layer may mean an average thickness of the cured layer excluding the height of wrinkles and protruding alumina formed on the surface.

The flooring material has a structure in which alumina particles protrude beyond a certain level on the surface of the hardened layer constituting the outermost layer, and may be used as an industrial flooring material used in an office or the like. In this case, the flooring material may include a substrate layer including ceramic tiles, rubber flooring, or polyvinyl chloride (PVC). For example, the base layer may be a transparent or translucent polyvinyl chloride (PVC) layer, and may have a thickness of about 1.0 mm to about 10.0 mm.

In addition, the flooring material may further include a foaming / non-foaming layer, a backing layer for stably attaching the flooring material, a glass fiber layer, and a printing layer in addition to the base layer and the curing layer. Specifically, the backing layer, the foaming / It may have a structure in which a non-foaming layer, a glass fiber layer, a printing layer, a base layer, and a curing layer are sequentially laminated in that order.

The flooring material has the above-described surface structure on the surface of the cured layer by applying the acrylic resin composition on one side of the base layer and sequentially irradiating short wavelength light in a specific range in three steps under different conditions to cure it. Flooring can be made.

Specifically, a first "light irradiation" step of partially curing the acrylic resin composition applied on the substrate layer by irradiating light having a wavelength of 200 nm to 400 nm in the air; A second "light irradiation" step of inducing "wrinkles" on the surface of the partially cured composition by irradiating light with a wavelength of less than 300 nm; And under nitrogen gas (N2) conditions, a third "light irradiation" step of irradiating light with a wavelength of 200 nm to 400 nm to the "wrinkle-induced composition on the surface to form a cured layer, which is a cured product"; may include. At this time, matters related to the structure of the substrate layer, the acrylic resin composition, and the surface of the cured layer are as described above.

Looking at each step of the manufacturing method is as follows.

First, the acrylic resin composition is applied on the base layer. The method of applying the acrylic resin composition may be performed by a method known in the art, for example, Mayer, D-bar, rubber roll, G / V roll ( G/V roll), air knife, slot die, microgravure, and the like.

In addition, the first light irradiation step is the first step of irradiating light to the composition applied on the substrate, and partially curing the composition by irradiating light with a wavelength of 200 nm to 400 nm to the acrylic resin composition in the air. This is a step of pre-curing the acrylic resin composition with a curing rate of 20 to 60% or 30 to 50%. Here, the curing rate can be confirmed through the intensity change of the stretching peak of the C=C bond through Fourier transform-infrared spectroscopy (FT-IR) measurement before and after the first light irradiation step of the acrylic resin composition.

In addition, the air condition may be performed under normal air or clean dry air conditions, and in some cases means a state in which oxygen gas (O ₂ ) is mixed with nitrogen gas (N ₂ ). can do. In this case, the concentration of the oxygen gas (O ₂ ) in the nitrogen gas (N ₂ ) may be 30 parts by volume or less with respect to 100 parts by volume of the entire mixed gas.

Through the first light irradiation step, the alumina particles included in the acrylic resin composition may have a structure protruding at a certain height by preliminarily curing before forming wrinkles on the surface of the acrylic resin composition. In addition, the shape of the wrinkles on the surface of the cured layer can be made small and uniform.

The second light irradiation step is a step in which the excimer generated by the irradiated light shrinks the surface of the acrylic resin composition and/or the surface treatment layer to form wrinkles, thereby increasing the scattering rate of light incident on the surface. The present invention can increase the light scattering rate by shrinking the surface of the composition and/or the surface treatment layer into a wrinkled structure using excimer, so that the glossiness of the surface treatment layer can be reduced without using a matting agent or with only a small amount of the matting agent. can To this end, the second light irradiation step may be performed in a nitrogen (N2) atmosphere, which is a non-reactive gas, using light having a wavelength of less than 300 nm, specifically, 100 to 200 nm or 150 to 195 nm having high energy, , In some cases, it may be performed in a nitrogen (N2) atmosphere containing a small amount of oxygen (O2), specifically, 1,000 ppm or less. In addition, in the second light irradiation step, the distance between the composition and the light source may be 50 to 150 mm.

In addition, the light irradiation amount in the second light irradiation step may be 5 mJ/cm 2 to 500 mJ/cm 2 , or, for example, 100 mJ/cm 2 to 500 mJ/cm 2 .

As an example, in the second light irradiation step, light having a wavelength of 172 ± 2 nm is applied to the composition to form an excimer in the composition, and nitrogen (N ₂ ) containing oxygen (O ₂ ) of 100 ppm or less is 295 to 295 It may be performed by irradiating for a very short time of 1 to 2 seconds with a light amount of 305 mJ/cm 2 (ie, light irradiation amount).

When the second light irradiation step is performed, the size and/or shape of the fine wrinkle structure formed on the surface of the cured layer can be easily controlled by controlling the gas condition, the distance between the composition and the light source, and/or the amount of light irradiation within the above range. .

And, the third light irradiation step is a step of additionally irradiating ultraviolet (UV) light to the wrinkled composition to completely cure the composition to 95% or more, with a wavelength of 400 nm or less, specifically a wavelength of 100 to 400 nm It can be performed in a nitrogen (N ₂ ) atmosphere using light. At this time, the surface temperature of the surface treatment layer may be 20 to 90 ℃.

For example, in the third light irradiation step, light having a wavelength of 300 ± 10 nm is applied to the cured layer with a light amount of 500 to 2000 mJ/cm 2 for a very short time of 1 to 2 seconds in a nitrogen (N ₂ ) atmosphere. It may be performed by irradiation, and at this time, the distance between the curing layer and the light source may be 100 ± 50 mm.

Light to be irradiated in the present invention may be irradiated according to a known method capable of irradiating light of a wavelength required for each step. For example, light having a wavelength of 400 nm or less in the UV region may be irradiated using a mercury or metal halide lamp.

In addition, in the present invention, the light irradiation time may be a very short time of 1 to 2 seconds, and the light irradiation time may be controlled by the speed at which the composition moves during light irradiation, for example, the speed of movement of the composition coated on the substrate. can For example, the moving speed of the substrate coated with the composition and/or the composition may be 1 to 50 m/min.

In the present invention, when the composition is cured, short-wavelength light in a specific range is used step by step under different conditions, so that a high curing rate can be exhibited even when a small amount of the initiator is included in the above range.

(Example)

Example 1:

Based on 100 parts by weight of the acrylic resin composition, 20.6 parts by weight of a monofunctional acrylic monomer mixed with isodecyl acrylate and lauryl acrylate and 1,6-hexanediol diacryl, a bifunctional acrylic monomer Acrylic monomer containing 12.3 parts by weight of late (1, 6 Hexanediol Diacylate), 12.3 parts by weight of bifunctional urethane acrylate oligomer (Mw 1,000 to 2,000), 4.1 parts by weight of bifunctional urethane acrylate oligomer (Mw 4,000 to 6,000), and 3 Urethane acrylic oligomer containing 12.3 parts by weight of functional urethane acrylate oligomer (Mw 6,000-8,000), 12.3 parts by weight of bifunctional silicone acrylate oligomer, 2.9 parts by weight of photoinitiator (Irgacure 184), 0.8 parts by weight of dispersant, 0.8 parts by weight of antifoaming agent, whey An acrylic resin composition was prepared by mixing 0.8 parts by weight of a tinting agent and alumina having an average particle diameter (D50) of 35 μm. At this time, the alumina was included in 20.6 parts by weight based on 100 parts by weight of the cured layer.

Then, the acrylic resin composition was applied to a polyvinyl chloride (PVC) substrate and fixed to a photocuring device. Thereafter, while moving the substrate at a moving speed of 9±0.5 m/min, the first light irradiation, the second light irradiation, and the third light irradiation are performed step by step to cure the MLS (multi-layer sheet) type substrate layer. And a non-foamed flooring specimen including a hardened layer was prepared. Specifically, the first light irradiation is performed by irradiating light with a wavelength of 250 to 400 nm under clean dry air conditions (O2 concentration: 20±2 vol.%) and a distance from the light source of 50±1 mm to 100 ± 2 mJ / cm 2 of irradiation, and the second light irradiation is performed under N2 conditions (O2 concentration: 1,000 ppm or less) and at a distance from the light source of 100 ± 1 mm, light with a wavelength of 172 ± 5 nm is 300 ±5 mJ/cm 2 of irradiation, and the third light irradiation was irradiated with light having a wavelength of 250 to 400 nm at an irradiation amount of 1000±10 mJ/cm 2 under N2 conditions and at a distance of 100±1 mm from the light source.

At this time, the average thickness of the cured layer was 15 μm.

Example 2:

Flooring specimens were prepared in the same manner as in Example 1, except that instead of the alumina of Example 1, alumina having an average particle diameter (D50) of 35 μm was mixed in an amount of 15 parts by weight relative to 100 parts by weight of the hardened layer.

Comparative Example 1:

Flooring specimens were prepared in the same manner as in Example 1, except that silica having an average particle diameter (D50) of 35 μm was mixed instead of the alumina of Example 1.

Comparative Example 2:

Flooring specimens were prepared in the same manner as in Example 1, except that instead of the alumina of Example 1, alumina having an average particle diameter (D50) of 10 μm was mixed.

Comparative Example 3:

Flooring specimens were prepared in the same manner as in Example 1, except that instead of the alumina of Example 1, alumina having an average particle diameter (D50) of 35 μm was mixed in an amount of 10 parts by weight relative to 100 parts by weight of the hardened layer.

evaluation

Experimental Example 1: Measurement of the surface structure of the cured layer

The flooring materials prepared in the above Examples and Comparative Examples were prepared as 5 specimens of 1 cmX1 cm, scanning electron microscope (SEM) analysis was performed on the specimens, and the results are shown in Table 1 below. Specifically, the average height of the alumina particles protruding on the surface of the hardened layer was measured by measuring the vertical distance from the tangent of the highest point of each of the protruding alumina particles to the surface of the hardened layer in a scanning electron microscope (SEM) image, and the protruding height of each particle. It was expressed as an average value divided by the number of protruding alumina particles.

The distance between the protruding alumina particles was measured in a scanning electron microscope (SEM) image, and the distance between any one alumina particle and the closest alumina particle was measured, and the average value was shown.

In addition, the surface roughness (Ra) of the surface of the hardened layer, excluding the alumina particles protruding from the hardened layer, was measured by placing the surface roughness measuring device (Mitutoyo SJ-210 model) and setting the built-in tip at a speed of 0.5 mm/s. Surface roughness was measured, and the maximum value, minimum value, and average value were expressed numerically.

Average height of protruding particles (μm) Average distance between protruding particles (μm) Average surface roughness of cured layer (minimum and maximum surface roughness) (Ra, μm) Example 1 8 70 3.3 (Min: 2.2, Max: 3.8) Example 2 7 110 3 (Min:2.6, Max:3.3) Comparative Example 1 8 85 3 (min: 1.5, max: 4.5) Comparative Example 2 1.5 90 0.9 (Min: 0.6, Max: 1.1) Comparative Example 3 7 350 2.5 (min:2, max:3)

Experimental Example 2: Gloss evaluation

The 60 ° gloss (gloss 60 ° condition) was measured using a gloss meter for the specimens of Examples and Comparative Examples, and the results are shown in Table 3.

Experimental Example 3: Scratch Resistance

In accordance with EN 16094:2012 B procedure, but using a weight of 6N instead of adding 4N, and rubbing 160 times with a medium fine hand pad (Scotch Brite SB7440) on the surface of the hardened layer, Scratch resistance under harsh conditions was evaluated.

It was visually confirmed whether scratches occurred on the rubbed surface and patterns due to the scratches were generated, and grades were given according to the criteria of EN 16094: 2012 described in Table 2 below. The evaluation results of the above Examples and Comparative Examples are shown in Table 3.

Experimental Example 4: Fouling Resistance

Conduct the test according to KS M 3802, but draw a line of about 10 cm on the surface using board marker, magic, and skid marks as contamination materials, and after 30 seconds, rub the drawn line with Kimwipes to remove the first contamination area standard The area remaining unerased (eg, traces or smears) was visually confirmed, and the results were classified according to the following criteria, and the results are shown in Table 3 below.

Grade 1: 90% or more of the remaining area based on the initial contaminated area

Grade 2: Remaining area based on the initial contaminated area is 60% or more and less than 90%

Grade 3: Remaining area based on the initial contaminated area is 20% or more and less than 60%

Grade 4: Remaining area based on the initial contaminated area is 5% or more and less than 20%

Grade 5: Less than 5% remaining area based on initial contaminated area

Experimental Example 5: Non-slip property

The results of measuring the "slip" resistance according to the ASTM E303 method are presented in Table 3 below.

Glossiness Harsh, scratch resistant stain resistance non-slip vod maca Magic skid marks Example 1 3 B2 5 5 5 53 Example 2 3 B3 5 5 5 48 Comparative Example 1 7 B5 5 3 5 45 Comparative Example 2 2 B5 5 5 5 35 Comparative Example 3 4 B4 5 5 5 38

As shown in Table 3, it can be seen that the flooring materials of the examples have excellent stain resistance, scratch resistance, and non-slip properties at the same time while exhibiting low gloss. On the other hand, Comparative Example 1 contains silica and has a structure similar to that of the present invention, but has high gloss and significantly reduced scratch resistance and stain resistance. And, Comparative Example 2 includes alumina particles having an average particle diameter, and the protruding height of the alumina particles is low, and wrinkles are formed due to the small particles, so the glossiness is lowered, but the scratch resistance is lowered , the non-slip properties were more significantly lowered. In Comparative Example 3, it can be confirmed that the distance between the alumina particles is long, the glossiness is high, and both scratch resistance and non-slip properties are reduced.

As described above, the present invention has been described with reference to the drawings illustrated, but the present invention is not limited by the embodiments and drawings disclosed in this specification, and various modifications are made by those skilled in the art within the scope of the technical idea of the present invention. It is obvious that variations can be made. In addition, although the operational effects according to the configuration of the present invention have not been explicitly described and described while describing the embodiments of the present invention, it is natural that the effects predictable by the corresponding configuration should also be recognized.

10: base layer
20: hardened layer
30: alumina

Claims (10)

base layer; and
Including; a cured layer of an acrylic resin composition having a plurality of alumina particles protruding on the surface,
The protruding average height of the alumina particles is 5㎛ to 10㎛
flooring.
According to claim 1,
The protruding height of each of the alumina particles is 19 μm or less
flooring.
According to claim 1,
The average distance between the alumina particles protruding on the surface of the hardened layer is 50 μm or more to less than 180 μm
flooring.
According to claim 1,
The average particle diameter (D ₅₀ ) of the alumina particles is 25 μm to 50 μm
flooring.
According to claim 1,
The alumina is included in an amount of 15 parts by weight to 30 parts by weight based on 100 parts by weight of the cured layer.
flooring.
According to claim 1,
In the cured layer, the average surface roughness (Ra) of the cured layer excluding protruding alumina particles is 2 μm to 4 μm.
flooring.
According to claim 1,
The acrylic resin composition includes an acrylic monomer, a urethane acrylic oligomer, a silicone-containing acrylic oligomer, a photoinitiator, and the alumina.
flooring.
According to claim 1,
When using a weight of 6N and evaluating micro scratch resistance according to EN 16094 B procedure, B3 grade or less
flooring.
According to claim 1,
The surface gloss is 3 or less under the condition of gloss 60 °
flooring.
According to claim 1,
The base layer includes one selected from the group consisting of polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, and combinations thereof
flooring.

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